Color developers containing competing developing agents



Jan. 24, 1967 E. T. PEscH ETAL 3,300,305

COLOR DEVELOPERS CONTAINING COMPETING DEVELOPING AGENTS Filed OCC. 25, 1962 m. Q. m. N.

O. N .LHSI'I G38 OJ. AllSNBO EDWARD T. PEscH REMSEN S. VAUGHN IN VEN TOR.

R a?, Ca/JL, fu/www@ ATTORNEY 8| AGENT United States Patent() f COLQR DEVELDPERS CONTAINlNG COMPETING DEVELOPING AGENTS Edward T. Pesch and Remsen S. Vaughn, Rochester, N.Y.,

,.assgnors to Eastman Kodak Company, Rochester, N.Y.,

a corporation ot New llersey Filed Get. 25, 1962,.Ser. No. 233,048

17 Claims. (Cl. 96,-22)

This invention is -related to a new class of competing developing agents and more particularly to their use in color` developers for reversal development of multilayer,

vmulticolor photographic elements.

Multilayer, multicolor photographic elements are well known in the art of color photography. Such elements usually have a support coated with a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer.

After exposure to light through an original image such elements are reversal developed by the steps: treatment with a black-and-white developer to develop a negative silver image in each image forming layer, selective re- ,exposure `ofthe red-sensitive layer with red light, treattive layer, treatment of the photographic element with a image in the layer that was green-sensitive and a yellow dye image in the layer that was blue-sensitive.

Thetcolor developers used for such photographic elements are usually aqueous alkaline solutions containing a pphenylenediamine type color developing agent having at least one primary amino group and a color forming coupler. Sodium sulte, sodium bromide, and other addenda are often used in these developer solutions. Usually phenolic or naphtholic couplers are used to form the cyanv dye image, pyrazolone couplers to form the .magenta dye image, and fopen chain ketomethylene couplers to form the yellow image.

It is known to use N-benzyl-p-aminophenol as a competing developing agent in the cyan developer solution to control the formation of cyan fog in the green-sensitive and the blue-sensitive layers of the photographic element during cyandevelopment. 4Many of the known compet- V ing developing agents have the `disadvantages that their oxidation products cause imagewise formation of a subs tantive green absorbing impurity which degrades the colonquality of greens and cyans by increasing the green absorption of the cyan image. ,-paminophenol, formed from N-benzyl-p-aminophenol The oxidation product,

causes this problem. y New competing developing agents are desired which will control cyan fogin lthe greenand blue-sensitive layers of the photographic element during cyan development` and will not produce oxidation products that form color absorbing `impurities that degrade. color quality.

` l It is, therefore, an object of our invention to provide a new class of competing developing agents which are used to advantage in cyan developers to give good cyan fog control in the green-sensitive and blue-sensitive layers dur- 3330y3oi5 Patented Jan. 24, 1967 Mice ing cyan development without forming green absorbing impurities which degrade the color quality of greens and cyans.

Another object is to provide improved cyan, yellow and magenta color developers which contain our competing developing agents.

Still further objects will be apparent from the following specication and claims.

These and other objects are accomplished according to our invention by using certain substituted p-aminophenols as competing developers in color developer solutions. The water-soluble competing developing agents oi:` our invention include those represented by the formulas:

wherein R and R1 each represents the hydrogen atom, or an alkyl group, such as methyl, ethyl, propyl, butyl, amyl,

,hexyl, heptyl, octyl, etc.; R2 :represents the hydrogen atom, a sulfoalkyl group, such as sulfomethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfohexyl, sulfoheptyl, etc., or an aminoalkyl group, such as aminomethyl, aminoethyl, aminopropyl, aminobutyL aminoamyl, aminohexyl, aminooctyl, etc., such that when R2 is the hydrogen atom, R1 is an ,alkyl group; n is an integer of from 1 to 8, such that in compounds of Formula I the total number of carbon atoms in the R, Rl and R2 groups taken together is not more than 8, and such that in compounds of Formula II the total number of carbon atoms in the two R groups and in the --(CH2),1- group taken together is not more than 8.

The following typical examples will serve to illustrate our water-soluble competing developing agents :but it` is to be understood that -our invention is not limited to these examples.

-H2S O 4 H-N-C H3 4-methylamino-2methylphen0l sulfate -CHa | H-N-C Hr- 2 N,N-ethylene bis (4-amino-2-methy1phen01) HaC-N-CHzSOsNa -4- N-methylJNsuIfomethylamino) phenol `sodium salt Our competing developing agents are used to advantage in color developer solutions for processing color photographic elements in instances where it is `desirable to control color contrast, fog, etc. The competing developing agents of our invention are unexpectedly better than some known competing developing agents and are valuable for use in color photographic processing. Our competing developing -agents are effective in the control of contrast and fog and are distinguished from some other compounds by forming oxidation products that do not produce color absorbing impurities which cause undesirable shifts in hue and/ or color contrast.

Our color developer compositions in their simplest form comprise (1) a color-forming coupler, (2) a primary aromatic amino developing agent, (3) a competing developing agent of our invention, (4) an-d an alkali.

We have found that it is advantageous to include a compound, such as diethyl hydroxylamine sulfate, diethyl hydroxylamine hydrochloride, etc. in the aqueous solution of the col-or developer com-position in order to extend the useful life of the developer especially during storage.

Our developer solutions may also contain any of the other addenda commonly used in color developer solutions, such as an alkali metal sulte, an alkali metal bromide, an alkali metal carbonate, an alkali metal bisulite, an alkali metal thiocynate an alkali metal iodide, etc.

The concentration of the competing developing agents can be varied considerably and will depend upon the particular coupler, the particular color developing agent and the particular competing developing agent to be used. The optimum concentration can be determined by methods Well known in the art, that is 'by making studies of the results given by systematic variations in concentration of these components.

Our competing developing agents are used to advantage in color developer solutions containing any of the well known primary aromatic amino silver halide developing agents, Isuch as the p-phenylenediamines including the alkyl phenylenediamines and alkyl toluene. diamines. These developing agents are usually used in the salt form such as the hydrochloride `or sulfate which are more stable than the amine. The p-aminophenols and their substitution products may also be used as color developing agents when the amine group is unsubstituted. The N-alkyl sulfonamido alkyl-p-phenylenediamine agents of U.S. Patent 2,193,015 are also very useful. All of the developing agents have an unsubstituted amino group which enables the oxidation product of the developer to couple with the color-forming products that form a dye image. Included among the color developers are, such typical illustrative examples as, 2-amino-5-diethylaminotoluene hydrochloride, N ethyl--methanesulfonamidoethyl-3 methyl 4-aminoaniline sulfate, 4-amino-N,Ndiethyl3 methylaniline hydrochloride, 4 amino N-ethyl-N-(- methanesulfonamidoethyl) m toluidine sesquisulfate monohydrate, 3-Inethyl-p-aminodiethylaniline sulfate, 4-

4 amino-N-ethyl-N-(-hydroxyethyl)aniline sulfate, N,N dimethyl-p-phenylenediamine hydrochloride, etc.

Any of the well known water-soluble coupler compounds can be used to advantage in our color developer solutions.

Cyan-forming couplers include the water-soluble couplers, such as the nitronaphthol couplers of Vittum et al., U.S. Patent 2,266,452 issued December 16, 1941 (e.g. S-nitrO-l-naphthol, etc.); the naphthol couplers of Porter et al., U.S. Patent 2,295,009 issued September 8, 1942 (e.g. 2cinnamoyllnaphthol, etc.); the hydroxy-naphthoic acid amide couplers of Salminen et al., U.S. Patent 2,313,586 issued March 9, 1943 (e.g. 1-hydroxy-2-naphthoic-N-methyl anilide, etc.); the 4sulfonamide group containing couplers of Vittum etal., U.S. Patent 2,362,598 issued November 14, 1944 (e.g. lo-(-naphthalenesulfonamino)phenol, etc.); the acylamino-phenol couplers of Vittum et al., U.S. Patent 2,369,929 issued February 20, 1945 (e.g. 2-phenylacetylamino-4-chloro-5-methylphenol etc.); the diacylaminophenol couplers of Salminen et al., U.S.Patent 2,772,162 issued November 27, 1956 (e.g. 2,5-diacetamidophenol, etc.); the coupler 2-(o-acetamido- IB-phenylethyl)-l-hydroxy naphthamide of Vittum et al., U.S. Patent 3,002,836 issued October 3, 1961; etc.

Magenta-forming couplers useful in our color developer solutions include the water-soluble couplers, such 'as the pyrazolones of Porter et al. U.S. Patent 2,311,082

issued February 16, 1943, and Reissue 22,329 June l, 1943 (e.g. 3-pacetaminoanilino-S-pyrazolone, etc.); the sulfonamide substituted pyrazolone couplers of Vittum et al., U.S. Patent 2,353,205 issued July 11, 1944 (e.g. l [p-(benzenesulfonamino)phenyl]-3-methyl-5-pyrazolone, etc.); the acylated amino pyrazolone couplers of Porter et al., U.S. Patent 2,369,489 issued February 13, 1945 (e.g. l-phenyl-3-acetamino-5-pyrazolone, etc.); the halogen-substituted pyrazolone couplers of Loria et al., U.S. Patent 2,600,788 issued June 17, 1952 (e.g. 1-(2,4,6 trichlorophenyl) 3 benzamido-S-pyrazolone, etc.) the pyrazolone couplers -of Porter et al., U.S. Patent 2,343,703 issued March 7, 1944 (e.g. 1-phenyl-3-anilino-S-pyrazolone, etc.); magenta couplers, such as 1-(2,4,6trichloro phenyl) 3-(4-nitrophenoxyacetamido)-5-pyrazolone, 1- (2,4,6 trichlorophenyl) -3- 4-nitroanilino -S-pyrazolone, etc. as described in Spath U.S. Patent 2,899,306 issued August 11, 1959; and the coumarone couplers, e.g., Mannes et al., U.S. 2,115,394, issued April 26, 1938, etc.

Yellow-forming couplers useful in our color developers include the water-soluble couplers, such as the couplers of Mannes et al., U.S. 2,108,602 issued February 15, 1938 (e.g. p benzoylacetoacetanilide, 1-acetoacetamiobenzimidazole, etc.); the couplers of Mannes et al., U.S. Patent 2,113,330 issued April 5, 1938 (e.g. benzoylacetone, acetylacetone, etc.); the sulfonamide substituted yellow couplers of Vittum et al., U.S. Patent 2,271,238 issued January 27, 1942 (e.g. p-(w-benzoylacetamino)-benzenesulfonamide, etc.); the sulfonic ester couplers of Porter et al., U.S. Patent 2,289,805 issued July 14, 1942 (e.g. methyl-p-(benzoylacetamido)|benzensulfonate, etc.); the couplers of Weissberger et al., U.S. Patent 2,439,352 issued April 6, 1948 (e.g. N-(benzoylacetyl)benzamde, N-(benzoylacetyl)acetamide, etc.); and many others.

Our color developer solutions containing the competing developing agents of our invention are unexpectedly 'better than the same solutions containing competing developing agents that are outside our invention. The following examples will serve to illustrate the advantages ob tained from use of our color developer solution.

EXAMPLE l Four pieces of a photographic element comprising a support coated with a red-sensitive silver halide emulsion layer were exposed to light through a step wedge (having 0.15 log exposure increments between consecutive steps) in a sensitometer. Each 0f these photographic 5 elements were treated with a black-and-white developer having the composition:

2,4-diamino phenol hydrochloride g Sodium sulfite g 50 Potassium bromide g 5 lWater l l to develop a silver negative image, the elements were Washed in Water, reexposed to red light and cyan developed in the solution described below to develop a silver positive and cyan dye positive image. One of these elements identified as A was cyan developed with a freshly mixed developer of our invention having the formula:

Cyan` developer 1 Sodium sulfite 10.0 Sodium bromide 2.5

Sodium sulfate 60.0 Potassium iodide 0.0-1 4-.amino-N-ethylN-(-hydnoxyetlhyl)-S-methyl aniline 2.0 1-hydroxy-2- (2-acetamido -phenylethyll napthamide 2.0 4-methylamino-Z-methylphenol sulfate .2 Water to l l.

Another element B was cyan developed with our developer 1 after it was aerated by passing a stream of air through it.

Element C was cyan developed with a freshly mixed developer like developer 1 lbut containing 0.2 g. of 4- lrnethylaminophenol sulfate in place of 4-methylamino- 2-metihylphenol sulfate.

Element D was cyan developed with the developer used to develop element C but after it was aerated by the same procedure described above.

The color developed elements lA, B, C and D were v treated with a conventional ferricyanide-bromide bleach followed by `a sodium thiosulfate fixing bath to remove silver halide and leave the cyan dye images. The optical densities of the step wedge dye images to red light and to green light were measured with a densitometer.

The accompanying drawings FIG. 1 and FIG. 2 illustrate the results obtained in Example 1.

FIG. 1 shows a -solid line curve which relates the density to red light and the density to green light measured for each step of element A processed through our freshly mixed cyan developer containing 4-methylamino- Z-methylphenol (i.e. 2methylNmethylpaminophenol), and a broken line curve which represents the correspond-` ing data for element B processed through our aerated cyan developer.

FIG. 2 shows a solid line curve which `relates the density to red light and the density to green light measured for each step of element C processed through freshlymixed developer differing from our cyan developer only by containing 4-methylaminophenol instead of 4-methylamino-2-methylphenol, and a broken line curve which represents the corresponding data for element D processed through the cyan developer used for element'C but after aeration.

A comparison of the curves in FIG. l shows that aeration, of our cyan developer containing 4-methylamino-2- methylphenol produced substantially no hue shift in the dye images formed on color development. This valuable characteristic of our developers is unexpected. A comparison of the curves in FIG. 2 shows that aeration of the cyan developer (outside our invention) whioh differed only from our cyan developer by containing 4-rnethylaminophenol sulfate (instead of its 2-methyl derivative) produced a very undesirable shift in the hue of the developed cyani-mage.

The other competing developing agents of our invention are also used in cyan developers that can be aerated without producing hue shifts in the developed dye image;`

'6 Yellow developer solutions and magenta developer solutions containing our competing developing agents show similar photographic stability` (that is, do not produce hue shifts or color contrast shifts in the developed dye image) upon aeration.

. EXAMPLE 2 Two pieces of a multilayer, multicolor photographic element containing three silver halide layers, one sensitive to red, one sensitive to green, and one sensitive to blue, such as Kodachrome film, were given identical eX- posures to Ilight through a step wedge (having 0.15 log exposu-re increments between consecutive steps) in a sensitometer.` Each of these elements was given negative development as in Example l, water washed, andthe redsensitive layers given .selective reexposure to red light. 4One element identified as 1 was then cyan-developed by treating it with a cyan developer having the formula:

Cyan developer 2 Water to 1 l.

The second element identified as 2 was cyan developed with a cyan developer 3 which was the same as `cyan developer 2 but contained 0.5 g. of- 4-methylaminophenol sulfate in place of 4-methylamino-Z-methylphenol sulfate. Both elements were then given identical processing comprising the following steps: water washing, selective reexposure of the blue-sensitive layer with blue light, yellow development in a developer having the formula:

Sodium sulfite (desiccated) 10.0

Sodium bromide 0.55

v Potassium iodide 0.026

N,N diethyl-p-phenylenediamine monohydrochloride 3 0 6-nitrobenzimidazolemirate 0.10

Sodium hydroxide 2.8 Polyethylene glycol (Carbowax 4000) 1.0 Sodium sulfate 64.0 Hexylene glycol 20.0 a-Benzoyl-o-methoxyacetanilide 1 1.5 Diethylhydroxylamine sulfate 1.38 1-phenyl-3-pyrazolidone ,A 0.50

Water to 1 l.

Then the elements were water washed, exposed to white light, developed in a magenta developer having the composition:

Trisodium phosphate 12H20 g 40.0` Sodium sulfite (-desiccated) g 5.0 Sodium trhiocyanate g 1.0

4-amino-N-ethyl-N IB-methanesulfonamidoethyU-m-toluidene sesquisulfate monohydrate g 2.9 Citrizinic acid g 0.72 Ethylenediamine g 3.0 Polyethylene glycol (Carbowax 4000) g 1.0 Sodium sulfate V g 50.0 Sodium hydroxide g 0.32

1- 2,4,6-trichlorophenyl) -3 (4-nitroanilino) -5- 7 pyrazolone g 1.67 Hexylene glycol ml 10.0 Sodium bromide g-- 0.5 Potassium iodide g 0.075

Water to 1 l.

water Washed, bleached in a ferricyanideJbromide bleach and fixed with a sodium thiosulfate fixing bat-h, washed and dried.

A comparison of the processed elements showed that the cyan image of element 1 processed with our cyan developer had satisfactory sharpness while the cyan image of element 2 processed with a cyan developer containing 4-methylaminophenol sulfate as the competing developing agent had very poor image sharpness.

EXAMPLE 3 Several pieces of fa multilayer, multicolor photographic element were exposed as in Example 2. These were given negative development with the black-and-white developer of Example 1, washed, and processed as described in Example 2 excepting that all the pieces of film were developed in a developer like cyan developer 2 of Example 2 and the iihns were given different yellow development. One piece of the film was yellow developed in our yellow devel-oper having the composition:

Sodium sulfte (desiccated) g 10.0 Sodium bromide g 0.22 Polyethylene glycol (Carbowax 4000) uuuu g 1.0 Potassium iodide g 0.01 N,N-diethyl-p-phenylenediamine monohydrochloride g 2.0 -nitrobenzimidazole nitrate n g 0.040 Trisodium phosphate-12H2O g 20.0 Sodium sulfate g 50.0 Hexylene glycol ml 20.0 a-benzoyl-o-methoxyacetanili-de g 2.0 Diethylhydroxylamine sulfate g 2.5 1-phenyl-3-pyrazolidone g 0.30 4-methylamino-Z-methylphenol sulfate g 0.35 Water to 1 1.

Other pieces of the lm were given the same development with the exception that the 4-methylamino-2-methylphenol s-ulfate concentration was varied by several 0.01 g./l. increments above and below 0.35 g./l. The other pieces of film were yellow developed with the same developer in which the l-phenyl-3-pyrazolidone and the 4-methylamino-2-methyl phenol sulfate were replaced with 4- methylaminophenol sulfate at concentrations of 0.23, 0.24, 0.25, 0.26 and 0.27 g./l.

A study of optical ydensity measurements made on the processed images showed that $0.01 g./l. variation .in the concentration of 4-methylaminophen-ol sulfate in the yellow developer gave significant photographic effects, while our yellow developer was much less sensitive to changes in the concentration of 4-methylamino-Z-methylphenol sulfate.

Microscopic examination of cross sections of lm samples showed that there was no silver retention in the yellow image layer of the film which was processed in our yellow developer while there was ya very high silver retention in the yellow image layer of the film processed in the yellow developer outside our invention.

EXAMPLE 4 A comparison was made lof our cyan developer 2 of Example 2 with a developer likeit which contained 4-N- benzylaminophenol sulfate instead of 4-methylamino-2- methylphenol sulfate after processing use, for the formation of dirt. No dirt problem was found in our developer even if the hydroxylamine sulfate was omitted from the solution. The other developer however showed a serious dirt problem unless hydroxylamine sulfate was present.

Our invention is still further illustrated by a description of the preparation of representative competing developing agents.

COMPOUND 1 To a solution of 955 g, of toluhydroquinone and 45 g. of sodium suliite in 3 l. of water which was `heated to 180 C. in an autoclave, were added 687 g. of 40% methylamine under nitrogen over a period of 3 hours. The autoclave was then `cooled to C. .and the contents were acidied with sulfuric acid. This solution was cooled to 15 C. whereupon a solid separated, was collected and dried, yielding 575 g. of product, M.P. 242*244 C.

COMPOU'ND 2 To a solution of 2 g. of lithium aluminum hydride in 400 ml. of anhydrous ethyl ether was added over a period of 15 hours at room temperature, a solution of 5 g. of N,Noxalyl bis(4-amino-2-methylphenol) in 500 ml. of anhydrous ethyl ether. After this time, aqueous :alcohol was added slowly to the mixture to decompose the excess hydride. The alumina which separated was dissolved by the addition of sodium potassium tartrate. The ether solution was separated, washed `with brine, dried and concentrated in vacuo. The solid residue was recrystallized from acetonitrile yielding 4.2 g. of Compound 2.

The N,N'oxalyl bis(4-amino-2-methylphenol) was prepared as follows. To a solution of 12 g. or 4-amino-2- methylphenol and 13 g. of quinoline in 125 ml. of diox-ane was added at room temperature with stirring, 6.3 g. of oxalyl chloride. The reaction mixture was stirred for 1 hour at room temperature, after which time the quinoline hydrochloride `was filtered olf. The filtrate was concentrated in vacuo, and the residue recrystallized from ethyl alcohol yielding 6.8 g. of N,Noxalyl bis(4amino2 methylphenol) COMPOUIND 3 A mixture of 35 g. of p-bromophenol, 40 g. of 60% ethylenediamine and 2 g. of copper sulfate penta hydrate, in ml. of water was reuxed for 6 hours after which time it was acidiiied with sulfuric acid. This mixture was concentrated to approximately 1A of the original volume and cooled to 15 C. whereupon a solid separated, was collected and dried, yielding 41 g. of product, M.P. 279- 280 C.

COMPOUND 4 To a neutralized solution (i.e. NaOH and Na2SO3) of 86 g. of 4-methylaminophenol sulfate in 500 ml. of water were added 75 g. of sodium formaldehyde sulte. This mixture was cooled until a com-plete solution resulted. The resultant solution was cooled to 15 C. whereupon a white solid separated, was collected Iand dried, yielding 101 g. of product.

The substituted 4-aminophenols of our invention are valuable competing developing agents for color developer solutions used in processing color photographs. Oui compounds are good for color contrast control, for preI venting the formation lof color fog in adjacent layers, for example, for preventing the formation of cyan fog in the blue-sensitive and in the green-sensitive layers during cyan development or preventing the formation of yellow fog in the magenta layer during yellow development, etc.

Our compunds are differentiated from other similar compounds when they are used as competing developing agents. For example, our color developers containing 4methylamino-2-methy1phenol sulfate do not produce hue shifts in the images formed with used or aerated developing solutions as do the corresponding used or aerated developer solutions containing 4-methylaminophenol sulfate (outside our invention). Certain of these 4-methylaminophenol containing developer solutions outside our invention produce images with poor sharpness and very high residual silver (even after bleaching and xing) while the corresponding developer solutions with and wherein R and R each represent groups selected from the class consisting of the hydrogen atom, andan alkyl group; RZ represents a group selected from the class consisting of the hydrogen atom, and an aminoalkyl group, such that when R2 represents the hydrogen atom, R is an alkyl group; and n is an integer of from lto 8, such that in compounds having Formula I, the total number of carbon atoms in the groups R, R' and R2 taken together is at least.2 'and not more' than 8, and such that in compounds having Formula II, the total number f carbon atoms in the two R groups and in the -(CH2) group is at least 2 and not more than 8.

2. A color developer'composition of claim 1 containing an alkali metal sulte, an alkali metal bromide, and an alkali metal iodide.

3. A color developer composition of claim 1 containing a color-forming coupler selected from the class consisting of the phenolic couplers, the naphtholic couplers, the pyrazolone couplers, the courmarone coupler, :and the open-chain ketomethylene couplers.

4. A color developer composition of claim 1 containing a primary aromatic amino developing agent selected from the class consisting of .a 4-aminophenol, and a p-phenylenediamine.

5. A color developer composition comprising (1) a primary aromatic amino developing agent, (2) a colorforming coupler, (3) an alkali, and (4) 4-methylamino- Z-methylphenol sulfate.

6. A color developer composition comprising 1) a primary aromatic amino developing agent, (2) a colorforming coupler, (3) an alkali, and (4) N,Nethylene bis (4-arnino-2-methylphenol) 7. A color developer composition comprising (1) a primary aromatic amino developing agent, (2) a colorforming coupler, (3) an alkali, and (4) 4-(-aminoethylamino) phenol sulfate.

8. A color developer composition comprising (1) a primary aromatic amino developing agent, (2) a colorforming coupler, (3) an alkali, and (4) 4-(N-methyl- N-sulfomethylamino)-phenol sodium salt.

9. A color developer composition comprising (l) 4-amino N ethyl-N-(-hydroxyethyl)-B-methylaniline, (2) 2-(o-acetamido--phenylethyl)-l-hydroxy naphthaf 10 mide, (3)"4-methylamino-2methylphenol, (4) an alkali, and (5 ),an alkali metal suliite.

10. A color developer composition comprising (l) N,Ndiethylp-phenylenediamine, (2) u benzoyl-o-methoxyacetanilide, (3) 4-methylamino-Z-methylphenol, (4) an alkali and (5) an alkali metal sulte.

11. A color developer comprising (l) 4-amino-N- ethyl-N-(,B-methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate, (2) 1-(2,4,6-trichlorophenyl)-3- (4-nitroanilino) 5 pyrazolone, (3) 4 methylamino-2- methylphenol, (4) an alkali, and (5) an alkali metal sulte.

12. In the color reversal development of a multilayer, multicolor photographic element after exposure to light through an original image, said element comprising a supported coated with differently sensitive silver halide emulsion layers, one of said layers being red-sensitive, one of said layers being green-sensitive and one of said layers being blue-sensitive, in which the said exposed element is given a negative black-and-white development, selective re-exposure of said red-sensitive layer with red light, treatment of said element with a cyan color developer, selective re-exposure of the said blue-sensitive layer with blue light, treatment of said element with a yellow color developer, fogging the uneXposed silver halide in the green-sensitive layer, treating the said element with a magenta color developer, treating said developed element in a ferricyanide-bromide bleach and then in a fixing bath, to leave in said element a color reproduction of said original image,the improvement in the said process comprising the use, in at least one of said color developers, of a water-soluble non-color-forming competing developing agent selected from those having the formula:

(I) on Rz-N-R' and wherein R and R each represent groups selected from the class consisting of the hydrogen atom, and an alkyl group; R2 represents a group selected from the class consisting of the hydrogen atom, and an aminoalkyl group, such that when R2 is the hydrogen atom, R' is an alkyl group; and n is an integer of from 1 to 8, such that in compounds having Formula I, the total number of carbon at-oms in the groups R, R and R2 taken together is at least 2 and not more than 8, and such that in compounds having Formula II, the total number of carbon atoms in the two R groups and in the -(CH2)ngroup is at least 2 and not more than 8.

13. In the lcolor reversal development process of claim 12 for a multilayer, multicolor photographic element, the improvement in the said process comprising the use of 4-methylamino-Z-methylphenol as a competing developing agen-t in the cyan developer solution.

14. In the color reversal development process of claim 12 for :a multilayer, multicolor photographic element, the improvement in the said process comprising the use of 4-methylamino-Z-methylphenol as a competing developing agent in the yellow developer solution.

15. In the color reversal development process of claim 12 for la multilayer, multicolor photographic element, the improvement in the said process comprising the use of 11 4-methylamino-2-methylphenol in the magenta developer solution,

16. A composition for preparing a color developer solution, said composition comprising (1) a primary aromatic amino `developing agent and (2) a water-soluble, noncolor-forming, competing developing agent selected from those having the formulas:

RLN-R' and wherein R and R each represent groups selected from the class consisting of the hydrogen atom, and an alkyl group; R2 represents a group selected from the class consisting of the hydrogen atom, and an aminoalkyl group, such that when R2 represents the hydrogen atom, R is Ian alkyl group; and n is an integer of from 1 to 8, such that in compounds having Formula I, the total number of carbon atoms in t-he groups R, R' and R2 taken together is at least 2 and not more than 8, `and such that in compounds having Fortmula II, the total number of carbon atoms in the two R groups and in the -(CH2)ngroup is at least 2 and not more than 8.

17. A composition for preparing a color devel-oper solution, said composition comprising (1) |a `color-forming coupler and (2) a water-soluble non-color-forming competing developing agent selected from those having the formulas:

R2-1lr-R' and (II) 0H 0H wherein R and R each represent groups selected from the class consisting of the hydrogen atom, and an alkyl group; R2 represents :a group selected from the 4class consisting of the hydrogen atom, and an aminoalkyl group, such that when R2 represents the hydrogen atom, R' is an alkyl group; and n is an integer -of from 1 to 8, such that in compounds having Formula I, the total number of carbon atoms in the groups R, R tand R2 taken together is at least 2 and not more than 8, tand such that in c0mpounds having Formula II, the total number of carbon atoms in the two R groups and in the -(CH2) group is at least 2 and not more than 8.

References Cited by the Examiner UNITED STATES PATENTS 1,978,433 10/1934 Major 96-66 2,301,381 11/1942 Dickey et a1. 96-55 2,319,078 5/1943 McNally et a1 96-66 2,368,255 1/1945 Lyon 96-66 2,397,676 4/1946l Lyon 96 66 2,594,917 4/1952 Gunther 96-55 3,134,673 5/1964 Gauguin et a1. 96-55 3,141,771 7/1964 Baird et a1 96-55 FOREIGN PATENTS 811,185 4/1959 Greatntain.

NORMAN G. TORCHIN, Primary Examiner.

I. T. BROWN, Assistant Examiner.

gg@ UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTION Patent NO 3.300.305 Dated Januarv 24. 1967 Inventor) Edward T. Pesch and Remsen S. Vaughn It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 9, line 5l, delete the term "courmarone" and substitute in its place --coumaron-.

Column l0, line l6, delete the word "sensitive" and substitute in its place senstzed-. I

iGNED ANU SEALED (SEAL) Attest:

EdmlMFletcher'J" WILLIAM E. 4summum-3E, JR. Attesting Officer Gummissioner of Patents 

12. IN THE COLOR REVERSAL DEVELOPMENT OF A MULTILAYER, MULTICOLOR PHOTOGRAPHIC ELEMENT AFTER EXPOSURE TO LIGHT THROUGH AN ORIGINAL IMAGE, SAID ELEMENT COMPRISING A SUPPORTED COATED WITH DIFFERENTLY SENSITIVE SILVER HALIDE EMULSION LAYERS, ONE OF SAID LAYERS BEING RED-SENSITIVE, ONE OF SAID LAYERS BEING GREEN-SENSITIVE AND ONE OF SAID LAYERS BEING BLUE-SENSITIVE, IN WHICH THE SAID EXPOSED ELEMENT IS GIVEN A NEGATIVE BLACK-AND-WHITE DEVELOPMENT, SELECTIVE RE-EXPOSURE OF SAID RED-SENSITIVE LAYER WITH RED LIGHT, TREATMENT OF SAID ELEMENT WITH A CYAN COLOR DEVELOPER, SELECTIVE RE-EXPOSURE OF THE SAID BLUE-SENSITIVE LAYER WITH BLUE LIGHT, TREATMENT OF SAID ELEMENT WITH A YELLOW COLOR DEVELOPER, FOGGING THE UNEXPOSED SILVER HALIDE IN THE GREEN-SENSITIVE LAYER, TREATING THE SAID ELEMENT WITH A MAGENTA COLOR DEVELOPER, TREATING SAID DEVELOPED ELEMENT IN A FERRICYANIDE-BROMIDE BLEACH AND THEN IN A FIXING BATH, TO LEAVE IN SAID ELEMENT A COLOR REPRODUCTION OF SAID ORIGINAL IMAGE, THE IMPROVEMENT IN THE SAID PROCESS COMPRISING THE USE, IN AT LEAST ONE OF SAID COLOR DEVELOPERS, OF A WATER-SOLUBLE NON-COLOR-FORMING COMPETING DEVELOPING AGENT SELECTED FORM THOSE HAVING THE FORMULA: 